CHM171L Physical Chemistry 2 Laboratory

4th Quarter AY 2015-2016

Thermodynamics of Mixture: Determination of Partial Molar

Enthalpy
Ricky Jay C. Gomez1
1Students, Mapúa Institute of Technology, School of Chemical Engineering and Chemistry

ABSTRACT

Partial molar quantity is very essential in determining extensive properties using different thermodynamic
correlations. It depends on other intensive properties such as the temperature and pressure but at varying molar
composition, the value for these intensive properties also change. Determining the partial molar enthalpy of
ammonium chloride- water solution was the focus of this experiment. The objectives were to determine the effect of
compositions of the mixture on the molar enthalpy of the solution and to evaluate the partial molar enthalpy of the
different components of the mixture. Using 6755 solution calorimeter, the enthalpies of the solution at varying
concentrations of the ammonium chloride (NH4Cl) and water (H2O) solution were determined. The amount of water
in the solution remain constant at 100ml while the amount of NH4Cl increases by 0.05 grams on every trial. The trend
of the curve fitted with the data shows an exothermic process occurred. This signifies the energy utilized for the
bond breaking process as water is being added, which outweighs the bond forming energy used for the formation of
ammonium chloride. The molar enthalpy of the solution decreases with the increasing mole fraction of the
ammonium chloride. In terms of the mole fraction of water, the molar enthalpy of solution is quite similar in terms
of the ammonium chloride, but has only a negative slope. The partial molar enthalpy of the ammonium chloride
increases with the increase in mole fraction while the partial molar enthalpy of water decreases with the increase in
its mole fraction.

Keywords: partial molar enthalpy, solutions calorimeter.

INTRODUCTION 𝜕𝑉
Vi = ( )T,p,n’ (2)
𝜕𝑛𝑖
Partial molar quantity is an intensive thermodynamic
property that describes how extensive property of
species changes with the variation of molar
composition at constant temperature and pressure. For the total volume of a binary mixture:
For a given extensive property X of the species i, the
partial molar quantity is defined as: V = nAVA + nBVB (3)
𝜕𝑋
Xi = ( )T,p,ni≠j (1)
µi = (
𝜕𝐺
)T,p,n’ (4)
𝜕𝑛𝑖
𝜕𝑛𝑖
The value for the partial molar quantity depends on
The fundamental equation for the chemical
the temperature, pressure and molar composition of
thermodynamics is defined by:
the mixture.

Some of the thermodynamic description of properties dG = Vdp – TdS + µAdnA + µBdnB +… (5)
defined by the partial molar quantity includes the
volume and Gibbs-Free Energy: The partial molar quantity for the properties such as
A, H and U is in terms of chemical potential, µ:

EXPERIMENT 05 | GROUP 05 | MAY 06, 2016 1

 𝜕𝑈
µi = ( )S,V,n’ (6)
𝜕𝑛𝑖
𝜕𝐻
µi = ( )S,p,n’ (7)
𝜕𝑛𝑖
𝜕𝐴
µi = ( )T,V,n’ (8)
𝜕𝑛𝑖
For a given mixture of two components A and B, the
measurement of the extensive properties is so tedious
and complicated. The rate of change of these extensive
properties is dependent in the change of other
properties such as the temperature, pressure and
composition. In order to have an accurate
measurement, partial molar quantities must be
measured at varying molar composition but all other
properties must be kept constant.
Thermodynamic properties vary at different molar
compositions because as the molecular environment
of such mixture changes by a fluctuating compositions,
partial molar quantities also change.
In this experiment, the partial molar enthalpy is
measured by varying the molar compositions at each
trial while keeping the pressure and temperature of
the environment held constant. The effect of
composition of the different components of the
mixture on the molar enthalpy of the solution should
be determined. Also, partial molar enthalpy of the
different components of the mixture must be
evaluated.
MATERIALS AND METHOD
Calorimeter. Distilled water and ammonium chloride
were the reagents used in this experiment.
Different amounts of ammonium chloride in terms of
mass were dissolve in water. Ten variations of
different ammonium chloride-water solution were
made with 0.05 g increment each trial, starting from
0.05 g to 0.5 g of solute ammonium chloride in same
volume of water.
At each trial, 100 g of water was measured and placed
in the Dewer flask. The Solution Calorimeter was set
up depending on the mass of the solute. Sample IDs
were also taken noted.
At the first beep of the calorimeter, the rod has been
pushed to fire the solute to the solvent. Second beep
indicated that the measurement of the Solution
Calorimeter has already been done.
The results of each trial were browsed and taken
noted. Same procedure was done for all of the trials.
From the data gathered, the molar enthalpy versus
concentration profile of the ammonium-water
solution has been prepared by simulating these data
in excel.
RESULTS AND DISCUSSIONS
Here is the plot of the mole fraction of NH4Cl versus
the molar enthalpy of solution:
Mole Fraction of NH4Cl vs Molar
Enthalpy
0
MOLAR ENTHALPY OF SOLUTION, CAL/MOL

0 0.0005 0.001 0.0015 0.002

-5000
The materials used
were 100 mL -10000 y = -3E+16x4 + 1E+14x3 - 2E+11x2 + 1E+08x - 47089
graduated cylinder, R² = 0.9105
-15000
evaporating dish,
wash bottle and 1L -20000
beaker. The
equipment used was -25000
PARR 1455 Solution -30000
FIGURE 1: PARR 1455 -35000
Solution Calorimeter.
-40000
MOLE FRACTION OF NH4CL

FIGURE 3: Mole Fraction of NH4Cl vs Molar Enthalpy

of Solution Curve.

FIGURE 2: Sample data gathered from the solution The generated curve fitting model for the
calorimeter. experimental data was based in the mole fraction of

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the ammonium chloride. From figure 3, obviously the
trend of the curve indicates that the solution exhibited Mole Fraction of Water vs Molar
an exothermic reaction. This signifies the energy Enthalpy of Solution
released in the bond-forming and bond-breaking 0
stage of the dissolution of ammonium chloride in

MOLAR ENTHALPY OF SOLUTION, CAL/MOL

0.998 0.9985 0.999 0.9995 1
-5000
water. At very dilute solution, the molar enthalpy of
the exothermic process obtains the highest value. As -10000 y = -3E+16x4 + 1E+17x3 - 2E+17x2 + 1E+17x - 3E+16
the amount of the solute increases in the solution, the -15000
R² = 0.8208
value for the molar enthalpy decreases gradually. This
gives the curve a fluctuating pattern, but still going on -20000
positive trend. The equation describes the complexity -25000
of the process, since the best equation of the trend line
-30000
reaches 4th power equation.
-35000
For the partial molar enthalpy of ammonium chloride, -40000
the curve fitting model is described by the curve: MOLE FRACTION OF WATER

Mole Fraction of NH4Cl vs Partial Molar FIGURE 5: Mole Fraction of Water vs Molar Enthalpy
Enthalpy of (a) of Solution Curve.
0
In figure 5, the curve for the molar enthalpy of solution
PARTIAL MOLAR ENTHALPY OF (A), CAL/G

0 0.0005 0.001 0.0015 0.002

-500000
in terms of the mole fraction of water is quite similar
y = -2E+15x4 + 5E+13x3 - 6E+11x2 + 8E+08x - 2E+06 with the curve in terms of the mole fraction of the
R² = 1 ammonium chloride, but the trend is just opposite, in
-1000000
which as the mole fraction of water increases, the
molar enthalpy of solution also increases.
-1500000

-2000000 Molar Fraction of Water vs Partial Molar

Enthaply of (b)
-2500000 0
MOLAR FRACTION OF NH4CL
PARTIAL MOLAR ENTHALPY OF (B), CAL/G

-2000.998 0.9985 0.999 0.9995 1

-400
FIGURE 4: Mole Fraction of NH4Cl vs Partial Molar 4 3 2
-600 y = 2E+14x - 9E+14x + 1E+15x - 9E+14x + 2E+14
Enthalpy of NH4Cl Curve. R² = 0.9969
-800

Figure 4 suggests that the slope of the curve denotes -1000

the partial molar enthalpy of ammonium chloride at -1200
its different molar composition. At very dilute -1400
ammonium chloride solution, the value for the partial
-1600
molar enthalpy for exothermic process decreases until
such point that the curve will start to have a negative -1800
MOLAR FRACTION OF WATER
slope. This signifies that the energy needed for the
exothermic process to proceed increases with the
increasing molar composition of ammonium chloride. FIGURE 6: Mole fraction of Water vs Partial Molar
Enthalpy of Water Curve.

Comparing the trend of the partial molar enthalpy of

water to that of the ammonium chloride, as the mole
fraction of water increases, the partial molar enthalpy
of water decreases while the partial molar enthalpy of
ammonium chloride is its exact opposite. Since partial
molar enthalpy is decreasing with the increasing mole
fraction of water, when it reaches the mole fraction

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equal to 1, no dissolution will occur since it is pure
water already and it is a one-component system.
Water added into water is just the addition of the
amount of substance.

CONCLUSION

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